CN105593431A - Permeable film, and method for producing the same - Google Patents

Permeable film, and method for producing the same Download PDF

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Publication number
CN105593431A
CN105593431A CN201480054720.4A CN201480054720A CN105593431A CN 105593431 A CN105593431 A CN 105593431A CN 201480054720 A CN201480054720 A CN 201480054720A CN 105593431 A CN105593431 A CN 105593431A
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breathable films
adhesive resin
glass
glass fabric
resin
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CN201480054720.4A
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CN105593431B (en
Inventor
山田宗纪
柴田健太
藤冈直史
竹内耕
繁田朗
江口寿史朗
细田雅弘
越后良彰
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Unitika Ltd
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Unitika Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Cell Separators (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides a permeable film which has even permeability and which exhibits excellent kinetic properties such as durability, and heat resistant properties such as shape stability at high temperatures. The present invention also provides a method for producing the permeable film. The permeable film is a permeable film in which a glass fiber fabric is impregnated with a binder resin, and is characterized by having the following features: (1) the binder resin covers the entire surface of the glass fiber fabric; and (2) the permeability of the permeable film is 1000 sec/100 cc or less and 1 sec/100 cc or more in Gurley values (JIS standard P8117). The method for producing the permeable film is also provided and is characterized in that the permeability of a glass fiber fabric is first eliminated by impregnating the glass fiber fabric that was opened with a binder resin, and then re-opening the glass fiber fabric.

Description

Breathable films and manufacture method thereof
Technical field
The present invention relates to Breathable films, specifically, relate to as lithium secondary battery and capacitorElectronic device substrate material, the liquid such as separator, electric substrate, chip package and circuit boardOr the useful Breathable films such as the filter of gas.
Background technology
Breathable films is for example widely used as the separator of lithium secondary battery and capacitor. SeparatelyOutward, also can be used as the electronic device substrate materials such as electric substrate, chip package and circuit board withAnd the filter of liquids and gases etc. and being widely used.
As the separator of lithium secondary battery, capacitor, conventionally can use formed by polyolefin saturatingGas film. For these polyolefin separator processed, if become the high temperature of 150 DEG C of left and right, easyCause contraction, fracture, therefore, according to circumstances anodal directly contact with negative pole and cause short circuit sometimes,Cannot suppress the abnormal heating causing because of short circuit. Therefore, even if seeking a kind of at such heightUnder temperature, also can fully guarantee the separator of insulating properties.
As the method that solves such problem, propose by polyester nonwoven or by being oxidizedIn the nonwoven that aluminium short fiber forms etc., impregnation coordinates Packed adhesive resin, thereby can composeGive the separator (for example, patent documentation 1,2) of the shape stability under high temperature.
But, in such method, under the rigidity low and high temperature as the nonwoven of base material itselfShape stability may not necessarily be abundant. The Breathable films that use obtains is as lithium secondary battery or electric capacityIn the situation of the separator of device, rigidity is low, likely causes and does not tolerate short circuit as separator and makeWith. In addition, use in the situation of nonwoven, the uniformity of the pore of formation is low, so can generateVentilative spot. If generate ventilative spot, cause the problems such as self discharge, therefore, do not tolerate as everyUse from part.
As eliminating the method for this problem, the good and gas of shape stability under a kind of high temperature is proposedThe separator of the use glass fabric having good uniformity in hole. For example, patent documentation 3,4Middlely proposed a kind of separator being made up of glass fabric, described glass fabric is containing being soaked withUtilize phase separation method to form the adhesive resin of microporous structure. In phase separation method, for example, willAdhesive resin and solvent are at high temperature mixed with the homogeneous solution T modulus method, the inflation method that formDeng carrying out after membranization, cooling it is separated, with other volatile solvent extraction except desolventizing,Form thus microporous structure. But, in such method, exist and setting containing being soaked with adhesiveIn the glass fabric of fat, easily produce pin hole etc. and make impaired this problem of uniform gas permeability.
Prior art document
Patent documentation
Patent documentation 1: No. 5213007 communique of Japan Patent
Patent documentation 2: No. 4743747 communique of Japan Patent
Patent documentation 3: TOHKEMY 2004-269579 communique
Patent documentation 4:WO2004/019433
Summary of the invention
Therefore, the object of the present invention is to provide the shape under the mechanical characteristics such as a kind of rigidity and high temperatureExcellent heat resistances such as stability and there is Breathable films and the manufacture method thereof of uniform gas permeability.
The inventor etc. further investigate in order to solve above-mentioned problem, found that, by usingFollowing Breathable films can solve above-mentioned problem, thereby has completed the present invention. Described Breathable films isUse adhesive resin that the glass fabric being made up of continuous long fibre is formed as specificallyStructure forms.
, purport of the present invention is as follows.
A kind of Breathable films containing being soaked with adhesive resin, has following spy in glass fabricLevy:
1) surface of above-mentioned glass fabric is by whole covering of adhesive resin;
2) air permeability of above-mentioned Breathable films counts 1000 with grignard value (JIS standard P 8117)Following 1 second of second/100cc/more than 100cc.
According to above-mentioned Breathable films, its rate of change with air permeability is the ventilative spot below ± 25%.
According to above-mentioned Breathable films, adhesive resin is that improved polyalkene is resin.
According to above-mentioned Breathable films, be in resin, to be combined with crosslinking agent at improved polyalkene.
The manufacture method of above-mentioned Breathable films, is characterized in that, is using by through opening fine process manyThe silk that individual glass fibre forms and impregnation adhesive resin in the glass fabric that forms makes glassAfter temporary transient disappearance of gas permeability of fabric, then open fine processing.
According to the manufacture method of above-mentioned Breathable films, wherein, then open fibre and be treated to the vibration in waterProcess.
According to the present invention, can provide the shape stability under characteristic and the high temperature of the mechanics such as a kind of rigidityDeng excellent heat resistance and there is the Breathable films of uniform gas permeability. Breathable films of the present invention canAs separator and electric substrate, chip package and electricity for the electric energy storage devices such as capacitor and capacitorThe electronic device substrate materials such as road plate.
Brief description of the drawings
Fig. 1 is the surface state that is illustrated in the glass fabric that uses in embodiment and comparative exampleMicrophotograph.
Fig. 2 is illustrated in embodiment 1 opening the impregnation adhesive resin that obtains before fine processing againThe microphotograph of the surface state of glass fabric.
Fig. 3 is the microscope that is illustrated in the surface state of the Breathable films finally obtaining in embodiment 1Photo.
Fig. 4 is illustrated in comparative example 1 opening the impregnation adhesive resin that obtains before fine processing againThe microphotograph of the surface state of glass fabric.
Detailed description of the invention
Below, the present invention is described in detail.
[Breathable films]
Breathable films of the present invention forms containing being soaked with adhesive resin in glass fabricBreathable films.
The glass fabric using in the present invention be use formed by multiple glass fibres silk andThe fabric forming. The composition of the glass fibre of glass fabric be not limited to alkali-free (E) glass,Low-k (D) glass, alkali (A) glass etc., but preferably taking alkali-free glass as raw materialGlass fabric. The preferred thickness of this glass fabric is below 50 μ m, more preferablyBelow 30 μ m, more preferably below 25 μ m. The lower limit of the thickness of glass fabricBe not particularly limited, but more than this thickness is generally 5 μ m, more than being preferably 10 μ m. Glass fibersThe thickness of dimensional fabric can be measured based on JISK7130-1992.
The average diameter that forms the glass fibre fibril of glass fabric is preferably below 5 μ m. GlassThe lower limit of the average diameter of glass fiber fibril is not particularly limited, but this average diameter is generallyMore than 1 μ m, more than being preferably 3 μ m.
The silk that forms glass fabric is preferably with public in No. 4192054 communique of Japan Patent for exampleThe method of opening is opened fine processing. As fiber opening method, can be known method, for example can liftGo out the vibration of the fiber opening method of the pressure based on water or other fluid, high frequency based on taking liquid as mediumFiber opening method of fiber opening method, processing based on utilizing roller to pressurize etc. Like this, by carrying outOpen fibre, can easily carry out resin impregnated to glass fabric.
The fabric tissue of glass fabric can use plain weave, twill-weave, satin weave etc.Any, be preferably tabby glass fabric.
In order to improve the interface affinity of glass fabric and adhesive resin, preferably even with silaneSurface treatment is carried out in connection agent etc. As silane coupler, can enumerate be selected from vinyl trichlorosilane,VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-metering systemAcyloxy propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-anilino-propyl group threeMethoxy silane, N-beta-aminoethyl-gamma-amino propyl trimethoxy silicane, N-vinyl benzyl-Amino-ethyl-gamma-amino propyl trimethoxy silicane (hydrochloride), γ-glycidoxy propyl group front threeTMOS, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-sulfydryl propyl group front threeIn TMOS and γ-r-chloropropyl trimethoxyl silane etc. more than a kind. In the present invention, onState silane coupler and be preferably N-vinyl benzyl-amino-ethyl-gamma-amino propyl trimethoxy silicane(hydrochloride) or γ-anilino-propyl trimethoxy silicane or their mixture. For makingWith the surface treatment of silane coupler, carry out as follows, that is, silane coupler is dissolved into conventionally approximatelyBe 0.01～20 quality % left and right, be preferably about the concentration of 0.1～5 quality % left and right, dissolvingImpregnated glass fiber or this fabric in the solution forming, after being hydrolyzed as required, heat.
The air permeability of the glass fabric using is in the present invention with based on JIS standard P 8117Grignard value meter is less than 1 second/100cc.
The quality of the per unit area of glass fabric is generally 10～40g/m2, be preferably15～35g/m2。
Above-mentioned glass fabric can utilize commercially available product. As commercially available product, can illustrate You Niji can strainFormula commercial firm glass fabric numbering processed E01Z, E01S, E02R, E03E etc.
The surface (above with two sides, the back side) of the above-mentioned glass fabric of Breathable films of the present inventionWhole is covered by adhesive resin. , by whole covering of adhesive resin for example, can pass through for whetherObtain its surface (above with two sides, the back side) with digit microscope (300 times of SEM multiplying powers)Digital image and judging. In this image, not observing area is completely 10 μ m2Above poreTime, can be judged to be whole of surface and be covered by adhesive resin. On the contrary, in this image, can be observedMore than one area is 10 μ m2When above pore, can judge and not be that whole by adhesive resin coatingLid. If can be observed more than one area 10 μ m2Above pore, uses Breathable films to doDuring for the separator of lithium secondary battery, can produce the problems such as self discharge.
In above-mentioned decision method, pore refers to, in the surperficial outward appearance of utilizing digital image to observeAbove, there is not the region of adhesive resin. Generally speaking, even impregnation in glass fabricAdhesive resin, sometimes local generation not by the region of impregnation (pin hole). On digital image,The region phase that has adhesive resin of the region that does not have adhesive resin like this and its peripheryRatio can clearly be distinguished in the difference of color, thickness etc. So, of the present invention ventilativeIn property film, one such, pore does not also exist.
In Breathable films of the present invention, although whole of the surface of glass fabric is set by adhesiveFat covers, but also has good gas permeability. Infer this be due to glass fabric silkForm due to the pore that is formed with even and fine linearity between fiber. Specifically, at thisIn bright Breathable films, whole of the surface of glass fabric is covered by adhesive resin, is formingAbundant filling adhesive resin between multiple glass fibres of the silk of glass fabric. Although due to asThere is adhesive resin in this place, but between glass fibre, be formed with and this glass between this glass fibreThe pore of fiber almost parallel, therefore, has good gas permeability.
The kind of the adhesive resin using in the present invention does not limit, for example, can enumerate modification polyeneHydrocarbon, Kynoar, polyacrylonitrile, PEO, polymethyl methacrylate, polyamides AsiaAmine, polyamide, polyamidoimide etc., can also mix them to use. In these, fromThe viewpoint of the cementability of glass fabric is considered, particularly preferably modified polyolefin resin.
Be resin as improved polyalkene, preferably use with respect to polyolefin have unsaturated carboxylic acid withoutThe copolymer of the structure that rule copolymerization or graft copolymerization form.
As becoming the polyolefinic concrete example that improved polyalkene is the skeleton of resin, can enumerate low closeDegree polyethylene, high density polyethylene (HDPE), polypropylene, ethene-butene-1 copolymer, ethylene-propylene are commonPolymers, polybutadiene etc.
Unsaturated carboxylic acid is that in 1 molecule, to have at least one free-radical polymerised key (particularly twoKey) and the unsaturated carboxylic acid of at least one carboxyl and its acid anhydrides. As its concrete example, can enumerate thirdOlefin(e) acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, aconitic acid,Aconitic anhydride, fumaric acid, crotonic acid, citraconic acid etc. Improved polyalkene is that resin can contain workFor the two or more compound of unsaturated carboxylic acid. From be easy to vistanex import viewpoint andGuarantee to consider with the viewpoint of the cementability with above-mentioned silane coupler glass fabric after treatment,Be preferably maleic anhydride, acrylic acid, methacrylic acid.
Improved polyalkene be resin also can be by utilizing interfacial polymerization, solution polymerization process, be suspended poly-The known method such as legal makes the monomer polymerization of regulation and manufactures, or can also serve as commercially available product withThe forms such as water is the water-based emulsion of main dispersing medium, solution taking organic solvent as primary solvent obtainArrive. Consider from the viewpoint of environment adaptability, improved polyalkene is that resin preferably uses water-based emulsion shapeThe resin of state. Improved polyalkene is that the water-based emulsion of resin for example can be used Japan Patent the 3699935thThe method manufacture of recording in number communique, No. 3759160 communique of Japan Patent etc. As commercially available product,Can illustrate Unitika Corp's system " arrobase " (trade name) numbering SA-1200,SB-1200, SE-1200, SB-1010 etc. Such commercially available product is that improved polyalkene is resinWater-based emulsion.
Be resin as improved polyalkene, can use composition, molecular weight and/or fusing point differentImproved polyalkene of more than two kinds is resin. Now, improved polyalkene of more than two kinds is that resin dividesNot in above-mentioned scope.
In order to improve heat resistance, be preferably in resin, to coordinate crosslinking agent at improved polyalkene.
Crosslinking agent is adhesive resin, and particularly improved polyalkene is the crosslinking agent of resin, for example,In 1 molecule, to there is the carboxyl that more than 2 can have with adhesive resin, sour anhydride groupThe organic compound (macromolecule that contains thermoplasticity or Thermocurable) of the reactive group of group's reaction.As the concrete example of crosslinking agent, can enumerateThe crosslinking agents such as azoles quinoline system, melamine series, epoxy system,Be preferablyAzoles quinoline is crosslinking agent.
Azoles quinoline is that crosslinking agent is to have more than 2 in 1 moleculeThe organic compound of azoles quinoline base(macromolecule that contains thermoplasticity or Thermocurable). AsAzoles quinoline is crosslinking agent, has Japan to urgeThe WS-700 of agent Co., Ltd. system etc.
Coordinate in the situation of crosslinking agent, from further fully guarantee adhesive resin impregnation amount andBetween the formation fiber of silk, further fully form the viewpoint consideration of the pore of linearity, crosslinking agentUse level with respect to adhesive resin particularly improved polyalkene be that resin is preferably 3～30 quality %,More preferably は 5～20 quality %. While using two or more crosslinking agents, their total coordinatesIn the scope of amount for above-mentioned use level.
In Breathable films of the present invention, the impregnation amount of adhesive resin is with respect to glass fabricBe preferably 5～40 quality %, more preferably 10～30 quality %. In adhesive resin, coordinateIn the situation of crosslinking agent, what the total impregnation amount of adhesive resin and crosslinking agent was adhesive resin containsThe amount of soaking.
In Breathable films of the present invention, air permeability is expressed as with grignard value (JIS standard P 8117)Following 1 second of 1000 seconds/100cc/more than 100cc, preferred air permeability is 600 seconds/100cc100 seconds below/more than 100cc. In the present invention, be that the meaning with such air permeability makesWith " gas permeability " this statement. Be as mentioned above by making air permeability, thereby as lithium secondary batteryWhile using separator, can guarantee good ion permeability. In the present invention, above-mentioned air permeability can be by adjustingThe impregnation amount of whole adhesive resin is controlled. Along with the impregnation amount of adhesive resin increases, above-mentionedAir permeability also increases thereupon.
The ventilative spot of Breathable films of the present invention, with respect to any 10 positions of Breathable filmsThe mean value of grignard value (JIS standard P 8117), be preferably ± below 25%, further preferredFor below ± 20%. By such setting, can guarantee uniform gas permeability. In the present invention, above-mentionedVentilative spot is by being used as the glass fabric of base material and carrying out fine processing of opening again described laterGuarantee.
As the heat resistance of Breathable films of the present invention, the preferably shape maintains under 150 DEG C of processingRate is more than 98%, more preferably more than 99%. Here, the shape maintains rate at 150 DEG C can be asLower calculating, is cut into 8cm × 8cm by Breathable films that is, carves therein the four directions of 6cm × 6cmShape, the baking oven of this Breathable films being put into 150 DEG C heats 30 minutes, measures the line of the film after heatingInterval. By aforesaid operations, for example, can use as thering are stable on heating lithium 2 primary cells wellSeparator uses. In the present invention, thereby on can guaranteeing as base material by use glass fabricState heat resistance.
[manufacture method of Breathable films]
For example, can easily obtain Breathable films of the present invention by following 3 operations.
The<the 1 operation>
Above-mentioned adhesive resin is made to solution or emulsion, for the preparation of being impregnated in above-mentioned glass fibreFabric containing immersion liquid (following, sometimes only referred to as " containing immersion liquid "). Can join containing in immersion liquid at thisClose state the organic macromolecule particulate such as crosslinking agent, polyolefin-based resins particle and aluminium oxide etc. byThe particulate that inorganic oxide forms etc. In addition, can coordinate emulsion stabilizer, various surface-activeAgent etc.
Adhesive resin concentration containing immersion liquid is not particularly limited. For example,, in adhesive resin concentrationCross thin and cannot realize the desirable impregnation amount of adhesive resin time, repeat containing in the 2nd operationSoak or be coated with and be dried.
The<the 2 operation>
, be dried and remove containing after immersion liquid impregnation or coating above-mentioned glass fabric above-mentionedSolvent or decentralized medium. Here, utilize impregnation or coating, in the gap of glass fabricFill containing immersion liquid. As concrete method, can preferably make with the following method: for example, by glass fibreTextile impregnation lifts after in above-mentioned solution or emulsion, uses mangle etc. to push liquidDip-coating method; Utilize mould, applicator roll solution or emulsion to be transferred to the transfer-type painting of supporting massThe known coating processes such as cloth method. Now, above-mentioned solution or emulsion can be knitted at glass fibreThe table back of the body surface of thing is coated with simultaneously.
As for the baking temperature except desolventizing or decentralized medium after impregnation, be preferably made as 50～150 DEG C. By such setting, can guarantee good the gluing of glass fabric and adhesive resinConnecing property. When dry, preferably make the gas permeability of the glass fabric after impregnation adhesive resin temporary transientDisappear. In order to reach this effect, the above-mentioned adhesive resin of impregnation in above-mentioned glass fabricTime, the impregnation amount of adhesive resin is 15～35 quality % with respect to glass fabric, preferablyBe 20～30 quality %. Thus, the table of whole cover glass fabric of adhesive resinFace and make gas permeability disappear. Here, " gas permeability disappearance " can whether exceed 2000 by grignard valueSecond/100cc judges. ,, when grignard value exceedes 2000 seconds/100cc, be judged as gas permeabilityDisappear, can confirm that surface is covered by adhesive resin by entire surface with the state that there is no pin hole etc. IfThe impregnation amount of the adhesive resin in this operation is very few, and the surface of the Breathable films finally obtaining is notCan fully be covered by adhesive resin, therefore, use this Breathable films as lithium secondary battery everyDuring from part, produce the problems such as self discharge. If the impregnation amount of the adhesive resin in this operation is too much,Even if carry out fine processing of opening again described later, the air permeability of Breathable films also can fully not reduce, because ofThis, as the not resistance to use of separator of lithium secondary battery. Coordinate crosslinking agent in adhesive resin time,The impregnation amount that the total impregnation amount of adhesive resin and crosslinking agent is adhesive resin.
The<the 3 operation>
The glass fabric of the impregnation adhesive resin that gas permeability is disappeared is opened fine processing again.In the glass fabric of impregnation adhesive resin, impregnation adhesive tree between the formation fiber of silkFat, by integrated multiple formation fibers. Open again fine processing and refer to, by least portion of this integrated fiberDivide and unscrew, forming the processing that forms substantially in parallel pore between fiber with this fiber. By like thisOperation, thus between the formation fiber of the silk of glass fabric, form the pore of uniform linearityRecover gas permeability, and can guarantee glass fabric uniformly ventilative of impregnation adhesive resinProperty.
As opening again the fine method of processing, compose by the glass fabric to impregnation adhesive resinGive vibration, as long as forming the pore that forms linearity between fiber, be just not particularly limited. Wherein,Preferably in water, give the vibration processing of vibration, for example, preferably use and in water, make tool irregularRotor and give the vibration processing device of vibration. As such vibration processing device, can exampleShow the former FV cleaning machine processed of KK. Komatsu Seisakusho.
The intensity of the vibration of giving is not as long as forming the pore that forms linearity between fiber, just haveSpecial restriction. For example, in the time that vibration is given in the rotation that utilizes the irregular rotor of tool, institute in waterThe intensity of the vibration of giving is preferably 400～1000rpm with this tachometer.
As long as can obtain the air permeability of above-mentioned regulation, to open again the fine treatment temperature of processing andProcessing time is not particularly limited.
The treatment temperature of the temperature of water etc. is generally 10～80 DEG C. In the present invention, Breathable films thoroughlyManner can be controlled by adjusting this treatment temperature. Treatment temperature is higher, Breathable films ventilativeDegree more reduces.
Vibration is given the processing times such as time and is generally 0.5～10 minute. In the present invention, gas permeabilityThe air permeability of film can be controlled by adjusting this processing time. Processing time is longer, Breathable filmsAir permeability more reduce.
As previously discussed, the glass fabric that forms Breathable films of the present invention shape at high temperatureShape stability is extremely good, be made up of, and rigidity is high continuous long fibre. In the present invention, like thisGlass fabric conventionally open and fine process and manufacture, in this glass fabric, impregnation is stickyMixture resin and make gas permeability temporarily disappear (the 2nd operation). Thereafter, then open fine processing (the3 operations). Therefore, Breathable films free of pinholes of the present invention etc., have uniform gas permeability and toolThere are high mechanical characteristic and heat resistance. Therefore, Breathable films of the present invention is applicable to for example, lithiumSeparator for secondary cell, separator, electric substrate, chip package and circuit board for capacitorDeng electronic device substrate material, and the filter of liquids and gases etc.
Below, enumerate embodiment, further illustrate the present invention. Should illustrate, the present invention alsoNot limited by embodiment.
[embodiment]
In embodiment and comparative example, the characteristic of Breathable films etc. are evaluated with following methods.
(1) thickness (unit: μ m)
The thickness of Breathable films is measured based on JISK7130-1992.
(2) air permeability (unit: second/100cc)
The air permeability (grignard value) of Breathable films is measured based on JISP8117.
(3) ventilative spot
Measure the air permeability of any 10 positions, place of Breathable films, calculating is inclined to one side from this mean valueRate, using its maximum or minimum of a value as rate of change. Be the situation below ± 20% by rate of changeBe judged to be to have good uniformity, by exceeding ± that 20% situation is judged to be uniformity is bad.
(4) utilize the surface coverage state of adhesive resin
Use and be assembled with at the VHX-1000 of Keyence company system (built-in optical lens)The digit microscope of VHX-D510 (built-in electronic lens), the surface of observing Breathable films is (frontFace and the back side) any 10 positions, place, obtain the digital image of 300 times of multiplying powers, do not observeArea is 10 μ m2When above pore, be judged to be surface and do not covered by entire surface by adhesive resinLid. On the contrary, in this image, can observe more than one area is 10 μ m2When above pore,Be judged to be not covered by entire surface by adhesive resin.
(5) heat resistance
Breathable films is cut into 8cm × 8cm, carves therein the square of 6cm × 6cm, will be byThe Breathable films of this formation is put into the baking oven of 150 DEG C and is heated 30 minutes. After heating by mensurationThe line interval of film, calculates heating shape maintains rate, evaluates thus, and this value is 98% when above,Be judged to be heat resistance good.
(embodiment 1)
The 1st operation:
Prepare tabby glass fabric (the quality 24g/m of per unit area2, thickness20 μ m, glass fiber diameter φ 4.1 μ m × 100 bundle, air permeability is less than 1 second/100cc, warpOpen fine processing and silane coupled processing). The microphotograph on glass fabric surface is shown in to figure1. On the other hand, the improved polyalkene of using as impregnation is resin, prepares improved polyalkene system treeThe water-based emulsion of fat is the numbering of Unitika Corp's system " arrobase " (trade name)SB-1200. In this water-based emulsion, addAzoles quinoline is crosslinking agent (Japanese catalyst Co., Ltd.WS-700 processed) stir, as uniform dispersion, preparation is containing immersion liquid. Here,AzolesQuinoline is that the use level of crosslinking agent is that resin (solid constituent) is made as 5.9 matter with respect to improved polyalkeneAmount %.
The 2nd operation:
Above-mentionedly above-mentioned glass fabric being flooded containing in immersion liquid of being diluted to appropriate concentrationProcess, push liquid with mangle, then, 80 DEG C dry 90 seconds, obtain with respect toGlass fabric contains the glass fabric of the adhesive resin that is soaked with 20.0 quality %. This glassThe air permeability of fabric exceedes 2000 seconds/100cc, confirms that gas permeability disappears. In addition, observeSurface coverage state, whole of result is covered by adhesive resin. By the glass of impregnation adhesive resinThe microphotograph of fabric surface is shown in Fig. 2.
The 3rd operation:
Next,, for the glass fabric of above-mentioned impregnation adhesive resin, use Co., Ltd.Little Songyuan City FV cleaning machine processed is given vibration 1 minute in the water of 70 DEG C, opens afterwards fine place againReason. Here as the rotating speed of FV cleaning machine, be made as 700rpm. The Breathable films obtainingAir permeability is 310 seconds/100cc, and ventilative spot is 15.2%, can confirm well and breathe freely uniformlyProperty. In addition, the heating shape maintains rate of this Breathable films is good, is 99.1%. Finally obtainThe total impregnation amount of the adhesive resin in Breathable films and crosslinking agent is with respect to glass fabricBe 20 quality %. Observe the result of the surface coverage state of Breathable films, set by adhesive for wholeFat covers. The microphotograph on Breathable films surface is shown in to Fig. 3.
(embodiment 2)
In the 2nd operation, the impregnation amount of adhesive resin is made as to 17 quality %, in addition,Carry out similarly to Example 1, obtain Breathable films. The glass fibre obtaining in the 2nd operationThe air permeability of fabric exceedes 2000 seconds/100cc, confirms that gas permeability disappears. In the 3rd operation, obtainThe air permeability of Breathable films be 256 seconds/100cc, ventilative spot is 17.5%, confirm good andGas permeability uniformly. In addition, the heating shape maintains rate of this Breathable films is good, is 98.8%.The total impregnation amount of the adhesive resin in the Breathable films finally obtaining and crosslinking agent is with respect to glassGlass fabric is 17 quality %. Observe the result of the surface coverage state of Breathable films, wholeCovered by adhesive resin.
(embodiment 3)
In the 2nd operation, the impregnation amount of adhesive resin is made as to 23 quality %, in addition,Carry out similarly to Example 1, obtain Breathable films. The glass fibre obtaining in the 2nd operation is knittedThe air permeability of thing exceedes 2000 seconds/100cc, confirms that gas permeability disappears. In the 3rd operation, obtainThe air permeability of Breathable films is 528 seconds/100cc, and ventilative spot is 14.3%, confirms good and equalEven gas permeability. In addition, the heating shape maintains rate of this Breathable films is good, is 99.3%. ?The total impregnation amount of the adhesive resin in the Breathable films obtaining eventually and crosslinking agent is with respect to glassFabric is 23 quality %. Observe the result of the surface coverage state of Breathable films, whole quiltAdhesive resin covers.
(comparative example 1)
In the 2nd operation, the impregnation amount of adhesive resin is made as to 10 quality %, in addition,Carry out similarly to Example 1 the impregnation processing of adhesive resin. Open again fine air permeability before treatmentBe 156 seconds/100cc, gas permeability does not disappear. Observe the glass fibers of this impregnation adhesive resinThe result of the surface coverage state of dimensional fabric, observing 2 areas is 10 μ m2Above pore,Being judged to be surface is not covered by entire surface by adhesive resin. By the glass fibers of this impregnation adhesive resinThe surperficial microphotograph of dimensional fabric is shown in Fig. 4. In addition, the glass of this impregnation adhesive resinThe ventilative spot of fabric is 35.2%, does not have uniform gas permeability.
(comparative example 2)
In the 2nd operation, the impregnation amount of adhesive resin is made as to 40 quality %, in addition, withEmbodiment 1 similarly carries out the impregnation processing of adhesive resin. Observe and open again fine surface before treatmentThe result of covering state, whole is covered by adhesive resin. Opening fine air permeability before treatment exceedes again2000 seconds/100cc, gas permeability disappeared.
Similarly to Example 1 the glass fabric of this impregnation adhesive resin is opened to fibre againProcess. Open again fine air permeability after treatment and exceed 2000 seconds/100cc, do not there is gas permeability. ?The total impregnation amount of the adhesive resin in the Breathable films obtaining eventually and crosslinking agent is with respect to glassFabric is 40 quality %. Observe the result of the surface coverage state of Breathable films, whole quiltAdhesive resin covers.
Shown in embodiment 1～3, the gas permeability excellence of Breathable films of the present invention,And shape maintains rate when 150 DEG C of heating is more than 98%, and grignard value rate of change is ± 25%Below, below particularly ± 20%. Therefore, the present invention requires heat resistance applicable to Breathable films(resistance to heat distorsion) and the uniformly lithium secondary battery of gas permeability and the separator of capacitor, electronicsThe mistake of the electronic device substrate materials such as substrate, chip package and circuit board and liquids and gasesFilter etc.
Utilizability in industry
Breathable films of the present invention can be used as separator, the electronics base of lithium secondary battery and capacitorThe filtration of the electronic device substrate materials such as plate, chip package and circuit board and liquids and gasesDevice etc.

Claims (6)

1. a Breathable films, in glass fabric containing being soaked with adhesive resin, have withLower feature:
1) surface of described glass fabric is covered by entire surface by adhesive resin;
2) air permeability of described Breathable films is counted with the grignard value based on JIS standard P 8117Following 1 second of 1000 seconds/100cc/more than 100cc.
2. Breathable films according to claim 1, the rate of change with air permeability is ± 25%Following ventilative spot.
3. Breathable films according to claim 1 and 2, wherein, adhesive resin is for changingProperty polyolefin-based resins.
4. Breathable films according to claim 3 wherein, is resin at improved polyalkeneIn be combined with crosslinking agent.
5. a manufacture method for the Breathable films described in claim 1～4, its feature existsIn, at impregnation adhesive resin in opening the fine glass fabric of processing, make glass fabricTemporary transient disappearance of gas permeability after, then open fine processing.
6. the manufacture method of Breathable films according to claim 5, wherein, then opens fine placeReason is the vibration processing in water.
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